CN106543215A - A kind of dinaphtho thiophene coughs up organic photoelectric functional material and its synthetic method - Google Patents
A kind of dinaphtho thiophene coughs up organic photoelectric functional material and its synthetic method Download PDFInfo
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- diiodonaphthalene
- dinaphthalene
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- dinaphtho thiophene
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- 239000000463 material Substances 0.000 title claims abstract description 36
- SYXXZXWLYNODHL-UHFFFAOYSA-N dinaphthothiophene Chemical compound C1=CC=CC2=C(C3=C(C4=CC=CC=C4C=C3)S3)C3=CC=C21 SYXXZXWLYNODHL-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 206010011224 Cough Diseases 0.000 title claims abstract description 24
- 238000010189 synthetic method Methods 0.000 title claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 42
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 40
- UYHYZAYIQAVJCN-UHFFFAOYSA-N 1,2-diiodonaphthalene Chemical compound C1=CC=CC2=C(I)C(I)=CC=C21 UYHYZAYIQAVJCN-UHFFFAOYSA-N 0.000 claims abstract description 25
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims abstract description 19
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 18
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims abstract description 14
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 5
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 5
- 239000001119 stannous chloride Substances 0.000 claims abstract description 5
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- QHODZFPKHGDLOS-UHFFFAOYSA-N 1,2,4,5-tetraiodobenzene Chemical class IC1=CC(I)=C(I)C=C1I QHODZFPKHGDLOS-UHFFFAOYSA-N 0.000 claims description 15
- 239000012074 organic phase Substances 0.000 claims description 15
- 239000003480 eluent Substances 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000004440 column chromatography Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000003810 ethyl acetate extraction Methods 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- FDTBOIISKGDAFB-UHFFFAOYSA-N 5-butylcyclopenta-1,3-diene zirconium(2+) Chemical compound [Zr++].CCCC[c-]1cccc1.CCCC[c-]1cccc1 FDTBOIISKGDAFB-UHFFFAOYSA-N 0.000 claims description 2
- -1 Methyl Chemical group 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000010828 elution Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 230000026045 iodination Effects 0.000 claims description 2
- 238000006192 iodination reaction Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 150000003754 zirconium Chemical class 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- BHASHBRUGOYKMC-UHFFFAOYSA-N 1,2,3,4-tetraiodobenzene Chemical compound IC1=CC=C(I)C(I)=C1I BHASHBRUGOYKMC-UHFFFAOYSA-N 0.000 abstract description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229910052740 iodine Inorganic materials 0.000 abstract description 3
- 239000011630 iodine Substances 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000002322 conducting polymer Substances 0.000 abstract description 2
- 229920001940 conductive polymer Polymers 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002685 polymerization catalyst Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 238000007445 Chromatographic isolation Methods 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 238000011097 chromatography purification Methods 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 6
- 239000000376 reactant Substances 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920003026 Acene Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 0 CCCCc1c(CCCC)c(cc(c(I)c2)I)c2c(C)c1* Chemical compound CCCCc1c(CCCC)c(cc(c(I)c2)I)c2c(C)c1* 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- POFAUXBEMGMSAV-UHFFFAOYSA-N [Si].[Cl] Chemical compound [Si].[Cl] POFAUXBEMGMSAV-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XVJWBXACABRAEC-UHFFFAOYSA-N benzene;1,1'-biphenyl Chemical group C1=CC=CC=C1.C1=CC=CC=C1C1=CC=CC=C1 XVJWBXACABRAEC-UHFFFAOYSA-N 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- PWYVVBKROXXHEB-UHFFFAOYSA-M trimethyl-[3-(1-methyl-2,3,4,5-tetraphenylsilol-1-yl)propyl]azanium;iodide Chemical compound [I-].C[N+](C)(C)CCC[Si]1(C)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 PWYVVBKROXXHEB-UHFFFAOYSA-M 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
- C07F7/0807—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms comprising Si as a ring atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
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Abstract
The invention discloses a kind of dinaphtho thiophene coughs up organic photoelectric functional material, mainly include with disubstituted interior alkynes as raw material the step of its synthesis, using the catalytic action of metallocene zirconium class complex, reacted by anhydrous and oxygen-free, synthesize a kind of zirconium heterocycle；Under the catalysis of stannous chloride, diiodonaphthalene is generated with tetraiodo-benzene；And then the lithiumation using n-BuLi is acted on, and synthesizes a kind of dinaphthalene；Under the last lithiumation in tert-butyl lithium is acted on, synthesis dinaphtho thiophene coughs up class photoelectric material.In synthesis technique, the coupling reaction of heterocyclic pentylene and polyaryl iodine is obtained diiodonaphthalene method simply, high income；By the activation of n-BuLi, dinaphthalene expeditiously can be synthesized by two molecule diiodonaphthalenes；It is as homogenous olefin polymerization catalyst, catalysis activity and all very high to the stereoselectivity of olefinic polymerization using metallocene zirconium class complex.The dinaphtho thiophene for synthesizing is coughed up has important use in conducting polymer composite, liquid crystal material and bioactivator field.
Description
Technical field
The present invention relates to organic photoelectric functional material field, and in particular to a kind of dinaphtho thiophene coughs up organic photoelectric functional material
And its synthetic method.
Background technology
As organic photoelectric functional material is in light emitting diode, solar cell, field-effect transistor, electricity storage, biochemistry
The application of the every field such as sensor, organic photoelectric functional material present swift and violent development trend in recent years.And with
What organic photoelectric functional material developed further gos deep into, and the difficult point of research essentially consists in the discovery and synthesis of pi-conjugated molecule.Closely
Since year, siliceous organic photoelectric functional material is of great interest, and many novelties, performance have been reported in the research for having correlation
The synthesis of excellent organic photoelectric functional material.Wherein, thiophene coughs up i.e. Silole, the outer σ of its silicon atom ring*Track and fourth two
The π of alkene*Track can form σ*-π*Conjugation, effectively reduces the lumo energy of system, improves electron affinity, so as to be beneficial to electricity
Son injection and transmission；And as silicon atom radius is larger, the key of formation easily polarizes, and bond energy is low, is easy to draw in synthesis
Enter injection and transport property that other functional groups with particular carrier transport property carry out modulating compound carrier.Cause
This, the study on the synthesis of the trapezoidal pi-conjugated molecule of acene containing silicon bridging is to research and development with unique electronic structure and light, electrical property
Organic photoelectric functional material is significant.
The trapezoidal pi-conjugated molecule of acene containing silicon bridging coughs up two class formations comprising phenyl ring and thiophene, and the quasi-molecule may be with sending out
The advantages of light efficiency, high carrier mobility.Silicon bridging is particularly simultaneously with regard to the trapezoidal pi-conjugated molecule of acene containing silicon bridging at present
The research report of benzene biphenyl is limited, and the related synthesis condition of silicon-containing material is typically harsher, and the synthesis of this kind of material is
Larger challenge and difficult task.
The content of the invention
The invention discloses a kind of organic photoelectrical material and its synthetic method, the invention with disubstituted interior alkynes as raw material, profit
With the catalytic action of metallocene zirconium class complex, reacted by anhydrous and oxygen-free, synthesize a kind of zirconium heterocycle；Then in stannous chloride
Under catalysis, diiodonaphthalene is generated with tetraiodo-benzene；And then the lithiumation using n-BuLi is acted on, and is reacted by anhydrous and oxygen-free, synthesis one
Plant dinaphthalene；It is last to react with dichlorodimethylsilane under the lithiumation effect of tert-butyl lithium, synthesize a kind of dinaphtho thiophene and cough up class light
Electric material.This material can effectively reduce the lumo energy of system, improve electron affinity, beneficial to electron injection and transmission, have
Unique electronic structure and light, electrical property.Meanwhile, the synthetic method is succinct, efficiently, and the raw material of reaction is easy to get, the system of intermediate
Standby process is stable, product is easy to modification and sense dough.
In order to solve above-mentioned technical problem, a kind of dinaphtho thiophene proposed by the present invention coughs up organic photoelectric functional material, formula
It is as follows：
In formula, R1Represent propyl group or butyl, R2Methyl or phenyl is represented, the compound is a kind of symmetric form dinaphtho thiophene
Cough up organic photoelectrical material.
Above-mentioned dinaphtho thiophene coughs up the synthetic method of type organic photoelectrical material, comprises the following steps：
The synthesis of step one, 1,2,4,5- tetraiodo-benzenes：It is with benzene as substrate, with periodic acid and KI as iodination reagent, dense
Sulfuric acid is solvent, at 0 DEG C reacts 24h, obtains the crude product of 1,2,4,5- tetraiodo-benzenes；2-methyl cellosolve is used after filtration washing
Recrystallization, obtains 1,2,4,5- tetraiodo-benzenes；
The synthesis of step 2, zirconium heterocyclic pentylene：Under conditions of anhydrous and oxygen-free, bis cyclopentadienyl zirconium dichloride and n-BuLi, -78 DEG C
Under the conditions of, reaction 1h generates dibutyl zirconocene, then reacts 3h with alkynes under room temperature, generates zirconium heterocyclic pentylene；
The synthesis of step 3, diiodonaphthalene：To in zirconium heterocyclic pentylene, addition stannous chloride, 1,3- dimethyl -3,4,5,6-
Tetrahydrochysene -2- pyrimidones and 1,2,4,5- tetraiodo-benzenes react 1h at 50 DEG C, use salt acid elution, then are extracted with ether, and deacidification is done
It is dry, filter, organic phase removes solvent, then with pure hexane as eluant, eluent column chromatography for separation, obtains diiodonaphthalene；
The synthesis of step 4, dinaphthalene：Diiodonaphthalene is taken under nitrogen protection, under low temperature, is taken n-BuLi and is added drop-wise to diiodonaphthalene
In, room temperature reaction 15h is quenched, ethyl acetate extraction organic phase, is dried, filters, remove solvent, with pure hexane as eluant, eluent
Column chromatography for separation, obtains dinaphthalene；
The synthesis that step 5, dinaphtho thiophene are coughed up：Dinaphthalene is added under nitrogen protection, under low temperature, takes tert-butyl lithium dropwise addition, room
Temperature reaction, then instills in the system of dichlorodimethylsilane, reacts 1 day, be quenched, extract organic phase, be dried, filter, remove away
Solvent, then with pure hexane as eluant, eluent column chromatography for separation, obtain dinaphtho thiophene and cough up；
Wherein, R22Representative has two R2Substituent.
Compared with prior art, the invention has the beneficial effects as follows：
The present invention with disubstituted interior alkynes as raw material, using the catalytic action of metallocene zirconium class complex, by anhydrous and oxygen-free
Reaction, synthesizes a kind of zirconium heterocycle；Under the catalysis of stannous chloride, diiodonaphthalene is generated with tetraiodo-benzene；And then using n-BuLi
Lithiumation is acted on, and is reacted by anhydrous and oxygen-free, synthesizes a kind of dinaphthalene；Under the last lithiumation in tert-butyl lithium is acted on, synthesize dinaphtho
Thiophene coughs up class photoelectric material.In synthesis technique, the coupling reaction of heterocyclic pentylene and polyaryl iodine is obtained diiodonaphthalene method simply,
High income；By the activation of n-BuLi, dinaphthalene expeditiously can be synthesized by two molecule diiodonaphthalenes；Using metallocene
Zirconium class complex is as homogenous olefin polymerization catalyst, catalysis activity and all very high to the stereoselectivity of olefinic polymerization.Synthesis
The dinaphtho thiophene for going out is coughed up has important use in conducting polymer composite, liquid crystal material and bioactivator field；This line
The pi-conjugated material of property, can be used as advanced electronics and photonic material.R bases in target product can be different alkyl, this
Outward, product can further derivatization, such as with Br or COOEt groups on phenyl ring, can proceed reaction makes product
Variation.Further structural modification, to synthesize several functions compound, can further should in organic photoelectric functional material field
With.
Specific embodiment
Technical solution of the present invention is described in further detail with reference to specific embodiment, described specific embodiment
Only the present invention is explained, not to limit the present invention.
Embodiment 1, a kind of dinaphtho thiophene cough up the preparation of organic photoelectric functional material, and step is as follows：
The synthesis of step one, 1,2,4,5- tetraiodo-benzenes：2.56g (11.2mmol) periodic acid is put in 250mL two-mouth bottles,
The 60mL concentrated sulfuric acids are added while stirring, are slow added into 5.58g (33.6mmol) KI, after 30min, are cooled the temperature to 0 DEG C, Xiang Qi
In be slowly added to 1mL (11.2mmol) benzene, under room temperature react 24 hours.Reactant liquor in bottle is poured on ice, is filtered, and is used methyl alcohol
Washing, obtains crude product.Recrystallized with 2-methyl cellosolve, obtain 1,2,4,5- tetraiodo-benzenes, yield 71%.
The synthesis of step 2, zirconium heterocyclic pentylene：Under nitrogen protection, 3.79g is added in 200mL reaction tubes
(13mmol)CpZr2Cl2, 50mL tetrahydrofurans are added, -78 DEG C are cooled to, addition 10mL (25mmol) n-BuLi, -78 DEG C
Reaction 1 hour.3.59mL (20mmol) 5- decine is added, is recovered to room temperature, is stirred 3 hours, obtain zirconium heterocyclic pentylene.
The synthesis of step 3, diiodonaphthalene a：Above-mentioned zirconium heterocyclic pentylene is cooled to into 0 DEG C, 1.18g (12mmol) chlorine is added
Change cuprous, 2.5ml (15mmol) 1,3- dimethyl -3,4,5,6- tetrahydrochysenes -2- pyrimidones (DMPU) and 5.28g (10mmol) 1,2,
After 4,5- tetraiodo-benzenes are warming up to 50 DEG C of reactions 1 hour, watery hydrochloric acid washing is added, add ether extraction, organic phase unsaturated carbonate
Hydrogen sodium solution is washed, and is dried, and is filtered, and revolving is except solvent.Column chromatographic isolation and purification, eluant, eluent are pure hexane, obtain structural formula such as
Under diiodonaphthalene a (3.5g, 58.3%).
The synthesis of step 4, dinaphthalene a：Under nitrogen protection, addition 0.906g (1.5mmol) diiodo- in 50mL reaction tubes
Naphthalene a, adds tetrahydrofuran 5mL.- 78 DEG C are cooled to, 0.3mL (0.75mmol) n-BuLi was added dropwise with three hours, room is risen to
Temperature, reacts 15 hours.Washed with watery hydrochloric acid, ethyl acetate extraction, organic phase are dried, and revolving is except solvent.Column chromatography analysis purifying,
Eluant, eluent is pure hexane, obtains 0.534g (yield 74.6%) dinaphthalene a, and the structural formula of dinaphthalene a is following.
The synthesis of step 5, target compound a：Under nitrogen protection, 0.7635g is added in 50mL reaction tubes
(0.8mmol) dinaphthalene a, adds 5mL tetrahydrofurans.- 78 DEG C are cooled to, 2.5mL (3.28mmol) tert-butyl lithium is added dropwise.Rise to
Room temperature, reacts 18 hours.Under nitrogen protection, reactant liquor is transferred in 100mL reaction tubes.Add in the reaction tube in advance
50mL tetrahydrofurans and 0.115mL (0.95mmol) dichlorodimethylsilane.Room temperature reaction 24 hours, washes with water, chloroform extraction
Take.Organic phase is dried, and revolving is except solvent.Column chromatographic isolation and purification, eluant, eluent are pure hexane, obtain 0.39g (yield 58.3%)
The following target compound a of structural formula, target compound a are dinaphtho thiophene and cough up organic photoelectric functional material.
Embodiment 2, a kind of dinaphtho thiophene cough up the preparation of organic photoelectric functional material, and step is as follows：
Step one, 1,2,4,5- tetraiodo-benzenes synthetic method it is same as Example 1.
The synthesis of step 2, zirconium heterocyclic pentylene：Under nitrogen protection, 3.79g is added in 200mL reaction tubes
(13mmol)CpZr2Cl2, 50mL tetrahydrofurans are added, -78 DEG C are cooled to, addition 10mL (25mmol) n-BuLi, -78 DEG C
Reaction 1 hour.2.88mL (20mmol) 4- octynes are added, is recovered to room temperature, is stirred 3 hours, obtain zirconium heterocyclic pentylene.
The synthesis of step 3, diiodonaphthalene b：Zirconium heterocyclic pentylene is cooled to into 0 DEG C, 1.18g (12mmol) protochloride is added
Copper, 3.0ml (18mmol) DMPU and 10.56g (20mmol) 1,2,4,5- tetraiodo-benzenes, is warming up to 50 DEG C, after reacting 1 hour, plus
Enter watery hydrochloric acid washing, add ether extraction, organic phase to be washed with saturated sodium bicarbonate solution, be dried, filter, revolving is except solvent.
Column chromatographic isolation and purification, eluant, eluent are pure hexane, obtain 3.94g (yield 65.6%) following diiodonaphthalene b of structural formula.
The synthesis of step 4, dinaphthalene b：Under nitrogen protection, addition 1.644g (3mmol) diiodonaphthalene in 50mL reaction tubes
B, adds 10mL tetrahydrofurans.- 78 DEG C are cooled to, 0.6mL (1.5mmol) n-BuLi were added dropwise with 1 hour, are warmed to room temperature,
Reaction 15 hours.Washed with watery hydrochloric acid, ethyl acetate extraction, organic phase are dried, and revolving is except solvent.Column chromatography analysis purifying, washes
De- agent is pure hexane, obtains the following dinaphthalene b of 0.439g (yield 34.7%) structural formula.
The synthesis of step 5, target compound b：Under nitrogen protection, 3.369g is added in 100mL reaction tubes
(4mmol) dinaphthalene b, adds 20mL tetrahydrofurans.- 78 DEG C are cooled to, 12.5mL (16.4mmol) tert-butyl lithium is added dropwise.Rise to
Room temperature, reacts 24 hours.Under nitrogen protection, reactant liquor is transferred in 200mL reaction tubes.The reaction tube is added in advance
100mL tetrahydrofurans and 0.575mL (4.75mmol) dichlorodimethylsilane.Room temperature reaction 30 hours, washes with water, chloroform extraction
Take.Organic phase is dried, and revolving is except solvent.Column chromatographic isolation and purification, eluant, eluent are pure hexane, obtain 1.542g (yield 54.1%)
The following target compound b of structural formula, target compound b are dinaphtho thiophene and cough up organic photoelectric functional material.
Embodiment 3, a kind of dinaphtho thiophene cough up the preparation of organic photoelectric functional material, and step is as follows：
Step one, 1,2,4,5- tetraiodo-benzenes of synthesis, its synthetic method are same as Example 1.
Step 2, synthesis zirconium heterocyclic pentylene, its synthetic method are same as Example 2.
The synthesis of step 3, diiodonaphthalene b：Zirconium heterocyclic pentylene is cooled to into 0 DEG C, 1.18g (12mmol) protochloride is added
Copper, 6.336g (12mmol) DMPU, 1,2,4,5- tetraiodo-benzene are warming up to 50 DEG C, after reacting 1 hour, add watery hydrochloric acid washing, plus
Enter ether extraction, organic phase is washed with saturated sodium bicarbonate solution, is dried, and is filtered, and revolving is except solvent.Column chromatographic isolation and purification,
Eluant, eluent is pure hexane, obtains 1.83g (yield 33.6%) diiodonaphthalene b.
The synthesis of step 4, dinaphthalene b：Under nitrogen protection, addition 3.29g (6mmol) diiodonaphthalene in 100mL reaction tubes
B, adds 25mL tetrahydrofurans.- 78 DEG C are cooled to, 1.2mL (3mmol) n-BuLi were added dropwise with 3 hours, are warmed to room temperature, instead
Answer 20 hours.Washed with watery hydrochloric acid, ethyl acetate extraction, organic phase are dried, and revolving is except solvent.Column chromatography analysis purifying, wash-out
Agent is pure hexane, obtains 1.68g (yield 66.7%) dinaphthalene b.
The synthesis of step 5, target compound c：Under nitrogen protection, 3.369g is added in 100mL reaction tubes
(4mmol) dinaphthalene b, adds 20mL tetrahydrofurans.- 78 DEG C are cooled to, 12.5mL (16.4mmol) tert-butyl lithium is added dropwise.Rise to
Room temperature, reacts 14 hours.Under nitrogen protection, reactant liquor is transferred in 200mL reaction tubes.The reaction tube is added in advance
100mL tetrahydrofurans and 0.986mL (4.75mmol) dichloro base silane.Room temperature reaction 20 hours, washes with water, chloroform extraction
Take.Organic phase is dried, and revolving is except solvent.Column chromatographic isolation and purification, eluant, eluent are pure hexane, obtain 0.954g (yield 33.5%)
Target compound c, gained target compound are dinaphtho thiophene and cough up organic photoelectric functional material.
Embodiment 4, a kind of dinaphtho thiophene cough up the preparation of organic photoelectric functional material, and step is as follows：
Step one, 1,2,4,5- tetraiodo-benzenes synthetic method it is same as Example 1.
Step 2, synthesis zirconium heterocyclic pentylene, its synthetic method are same as Example 1.
The synthesis of step 3, diiodonaphthalene a, its synthetic method are same as Example 1.
The synthesis of step 4, dinaphthalene a, its synthetic method are same as Example 1.
The synthesis of step 5, target compound a：Under nitrogen protection, 0.7635g is added in 50mL reaction tubes
(0.8mmol) dinaphthalene a, adds 5mL tetrahydrofurans.- 78 DEG C are cooled to, 2.5mL (3.28mmol) tert-butyl lithium is added dropwise.Rise to
Room temperature, reacts 18 hours.Under nitrogen protection, reactant liquor is transferred in 100mL reaction tubes.Add in the reaction tube in advance
50mL tetrahydrofurans and 0.197mL (0.95mmol) dichloro base silane.Room temperature reaction 24 hours, washes with water, chloroform extraction
Take.Organic phase is dried, and revolving is except solvent.Column chromatographic isolation and purification, eluant, eluent are pure hexane, obtain 0.26g (yield 45.4%)
The following target compound d of structural formula, target compound d are dinaphtho thiophene and cough up organic photoelectric functional material.
In the structural formula of the various embodiments described above, Pr is propyl group, and Bu is butyl, and Me is methyl, and Ph is phenyl.
To sum up, in the present invention, during dinaphthalene lithiumation, the reaction time is controlled in 14-24 hours, wherein reacting 18h
Left and right preferably, as the lithiumation effect of tert-butyl lithium is very strong, extends reaction time on yield and does not have too much influence.With chlorine silicon
When alkane reacts, the reaction time is 20-30h, wherein reaction 24h or so is preferably, the same reaction time yield that extends is without too big
Change.Reaction add tert-butyl lithium amount for dinaphthalene 4 times of equivalents, this be due to tert-butyl lithium and dinaphthalene reaction after, generate
Butyl iodide can and solvent in tert-butyl lithium reaction, add slight excess of tert-butyl lithium to be to make dinaphthalene lithiumation more thorough
Bottom, so as to improve the yield of reaction.
In the present invention, during dinaphthalene being generated by diiodonaphthalene, drip room temperature reaction 15-20 hours after n-BuLi,
Wherein reaction time 15h or so is optimal, extends the reaction time, and reaction yield is not varied widely.Be added dropwise n-BuLi when
Between for 3h when yield it is preferable, it may be possible to when n-BuLi rate of addition is too fast, on the diiodonaphthalene molecule of part, two iodine are simultaneously by lithium
Change, so while and some diiodonaphthalene be not lithiated, therefore generate dinaphthalene amount be greatly reduced.Meanwhile, dropwise drip
Plus the temperature of reaction system should be controlled at -78 DEG C during n-BuLi, because n-BuLi can occur with solvent THF when temperature is raised
Reaction.
Although invention has been described above, above-mentioned specific embodiment is the invention is not limited in, on
The specific embodiment stated is only schematic rather than restricted, and one of ordinary skill in the art is the present invention's
Under enlightenment, without deviating from the spirit of the invention, many variations can also be made, these belong to the present invention protection it
It is interior.
Claims (2)
1. a kind of dinaphtho thiophene coughs up organic photoelectric functional material, it is characterised in that：It is the following compound of formula,
In formula, R1Represent propyl group or butyl, R2Methyl or phenyl is represented, the compound is that a kind of symmetric form dinaphtho thiophene has been coughed up
Machine photoelectric material.
2. a kind of dinaphtho thiophene as claimed in claim 1 coughs up the synthetic method of type organic photoelectrical material, it is characterised in that include with
Lower step：
The synthesis of 1,2,4,5- tetraiodo-benzenes：With benzene as substrate, with periodic acid and KI as iodination reagent, the concentrated sulfuric acid is solvent,
24h is reacted at 0 DEG C, obtain the crude product of 1,2,4,5- tetraiodo-benzenes；Recrystallized with 2-methyl cellosolve after filtration washing, obtained
1,2,4,5- tetraiodo-benzenes；
The synthesis of zirconium heterocyclic pentylene：Under conditions of anhydrous and oxygen-free, bis cyclopentadienyl zirconium dichloride and n-BuLi, under the conditions of -78 DEG C, reaction
1h generates dibutyl zirconocene, then reacts 3h with alkynes under room temperature, generates zirconium heterocyclic pentylene；
The synthesis of diiodonaphthalene：To in zirconium heterocyclic pentylene, stannous chloride, 1,3- dimethyl -3,4,5,6- tetrahydrochysene -2- pyrimidines are added
Ketone and 1,2,4,5- tetraiodo-benzenes react 1h at 50 DEG C, use salt acid elution, then are extracted with ether, and deacidification is dried, and filters, organic
Solvent is mutually removed, then with pure hexane as eluant, eluent column chromatography for separation, obtains diiodonaphthalene；
The synthesis of dinaphthalene：Diiodonaphthalene is taken under nitrogen protection, under low temperature, is taken n-BuLi and is added drop-wise in diiodonaphthalene, room temperature reaction
15h, is quenched, ethyl acetate extraction organic phase, is dried, filters, remove solvent, with pure hexane as eluant, eluent column chromatography for separation,
Obtain dinaphthalene；
The synthesis that dinaphtho thiophene is coughed up：Dinaphthalene is added under nitrogen protection, under low temperature, is taken tert-butyl lithium and is added dropwise, room temperature reaction, then
Instill in the system of dichlorodimethylsilane, react 1 day, be quenched, extract organic phase, be dried, filter, remove away solvent, then with pure
N-hexane is eluant, eluent column chromatography for separation, obtains dinaphtho thiophene and coughs up；
Wherein, R22Representative has two R2Substituent.
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| CN107382782A (en) * | 2017-06-20 | 2017-11-24 | 绍兴文理学院 | A kind of synthetic method of polyaryl substituted naphthol derivative |
| WO2021177144A1 (en) * | 2020-03-04 | 2021-09-10 | 国立大学法人東海国立大学機構 | Naphthyl silole production method, naphthyl silole having heterocyclic group, and graphene nanoribbons having heterocyclic group |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107382782A (en) * | 2017-06-20 | 2017-11-24 | 绍兴文理学院 | A kind of synthetic method of polyaryl substituted naphthol derivative |
| CN107382782B (en) * | 2017-06-20 | 2020-05-12 | 绍兴文理学院 | Method for synthesizing polyaryl substituted naphthol derivative |
| WO2021177144A1 (en) * | 2020-03-04 | 2021-09-10 | 国立大学法人東海国立大学機構 | Naphthyl silole production method, naphthyl silole having heterocyclic group, and graphene nanoribbons having heterocyclic group |
| CN115210245A (en) * | 2020-03-04 | 2022-10-18 | 国立大学法人东海国立大学机构 | Preparation method of naphthyl silole, naphthyl silole with heterocyclic group and graphene nanoribbon with heterocyclic group |
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Application publication date: 20170329 |